Solubilized chromium salt in polymerization catalyst

ABSTRACT

A chromium salt such as ammonium chromate or ammonium dichromate, which is normally insoluble in nonaqueous solvents which do not easily rehydrate the silica surface is solubilized, for instance by treating it with a crown ether, and impregnated onto a particulate support from a nonaqueous solvent which does not easily rehydrate the silica. The resulting composition is then activated in an oxygen ambient such as air in a conventional manner and then utilized as a catalyst for polymerization reactions such as the production of polyolefins.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of copending application Ser. No.103,686, filed Dec. 4, 1979, U.S. Pat. No. 4,333,860.

BACKGROUND OF THE INVENTION

This invention relates to preparation of chromium-containing olefinpolymerization catalysts.

Supported chromium oxide catalyst can be used to prepare olefin polymersin a hydrocarbon solution or diluent to give a product having excellentcharacteristics from many standpoints.

The chromium can be incorporated into the support in several differentways which are well known in the art. One such method involvescoprecipitating a chromium compound with the support, for instance, byincluding a chromium compound in a silicate and thereafter combiningsame with an acid to form a gel. Frequently, the chromium compound isintroduced by means of an aqueous impregnation of the support followedby removal of the water. Because water has an effect on the porestructure and/or surface of silica which is generally adverse, it issometimes desirable to incorporate the chromium compound by means of ahydrocarbon solution of a soluble zerovalent chromium compound such asdicumene chromium. Finally, the chromium compound can simply bephysically mixed with the support, for instance by dry milling thesupport and the chromium compound.

Each of these means for incorporating chromium results in a catalysthaving different characteristics even though after the activation thechromium may be oxidized to the same chromium oxide form. This isbecause the pore structure and/or surface of the support may be affectedby the manner of chromium addition. Particularly, in the aqueousimpregnation of chromium, the pore structure of the support may bedamaged by the water, particularly by the removal of the water. Inaddition, water, primary alcohols and other materials which easilyrehydrate the silica surface can have an adverse effect on the resultingcatalyst and thus are not suitable solvents. However, this cannot beovercome simply by utilizing a hydrocarbon or other nonaqueous solutionsince ionic chromium compounds are generally insoluble in the type ofnonaqueous solvents which do not easily rehydrate the silica surface.The use of an alcohol to dissolve a chromium compound such as CrO₃ isnot always desirable either for the reason that the OH groups of thesolvent may react with the silica or the solvent reacts with thechromium compound.

SUMMARY OF THE INVENTION

It is an object of this invention to achieve a catalyst having thecharacteristics associated with aqueously impregnated chromium withoutthe necessity for introducing water or other solvents which tend toeasily rehydrate the silica surface;

It is a further object of this invention to simplify the impregnation ofchromium compounds into particulate supports by eliminating the need forcareful removal of water;

It is yet a further object of this invention to utilize a normally ionicchromium compound in an impregnation using a nonaqueous solvent whichdoes not easily rehydrate the silica surface;

It is still yet a further object of this invention to provide chromiumcatalysts having the chromium incorporated by nonaqueous means whichcatalyst is similar in characteristics to one produced by aqueousimpregnation of the chromium.

In accordance with this invention, a chromium salt which is insoluble innonaqueous solvents which do not easily rehydrate a silica surface, istreated with a solubilizing agent to convert it to a composition whichis soluble in nonaqueous solvents which do not easily rehydrate thesilica and the thus solubilized composition is thereafter impregnatedonto a particulate support from a solution and activated to produce acatalyst.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The catalysts of this invention are formed from a support and asolubilized chromium salt formed by contacting a chromium salt, which isinsoluble in nonaqueous solvents which do not easily rehydrate a silicasurface, with a solubilizing agent. The resulting composition is thencalcined in an oxygen ambient so as to convert at least a portion of thechromium to chromium oxide. The salts solubilized in accordance withthis invention possess charged ions as compared with the neutralcompounds such as π-bonded organochromium compounds which areconventionally added in an anhydrous solution.

The support is generally a particulate material selected from silica ora silica-containing material such as silica-alumina, silica-boria,silica-thoria, silica-titania, silica-zirconia, and other refractorymaterials and mixtures thereof. Particularly suitable are silica gelsprepared by coprecipitating a silicate and a titanium compound to form ahydrogel (titanium cogel) and then drying to form a silica xerogel asdisclosed in Dietz, U.S. Pat. No. 3,887,494 (June 3, 1975), thedisclosure of which is hereby incorporated by reference.

The presently preferred solubilizing agents are macrocyclic polyethercompounds (crown ethers). The macrocyclic polyether compounds are knownand they can be prepared as described in U.S. Pat. No. 3,687,978 whichissued Aug. 29, 1972 to Charles John Pedersen and in an article byPedersen in the Journal of the American Chemical Society 89 (26),7017-7037 (1967), the disclosures of which are hereby incorporated byreference. Suitable polyether compounds employable in this inventionpreferably contain from about 4 to about 10 oxygen atoms in the ring,each oxygen atom preferably being separated from the next one by linksof 2 carbon atoms. The macrocyclic ring can also be joined to 1 to 4carbocyclic rings selected from among phenylene, naphthylene,phenanthrylene, and anthrylene, their hydrogenated analogs, e.g.cycloalkylene, and substituted derivatives of the foregoing wherein thesubstituents are selected from among halo, nitro, amino, azo, alkyl,cyano, hydroxy, carboxy and sulfo. Generally, each substitutedderivative contains no more than about 30 atoms. A presently mostpreferred group of polyether compounds for use when the cation of thechromium salt is ammonium is that which contains 6 oxygen atoms in themacrocyclic ring. While not wishing to be bound by theory, it isbelieved the invention works as a result of the solubilizing agentphysically surrounding the cation of the chromium salt and reducing itspolarity. Thus the resulting material may not be a complex in the usualsense of the word, but the word complex is nevertheless used herein todescribe the solubilized composition. Specific examples of these include18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), dibenzo-18-crown-6(2,3,11,12-dibenzo-1,4,7,10,13,16-hexaoacyclooctadeca-2,11-diene), anddicyclohexano-18-crown-6(2,3,11,12-dicyclohexano-1,4,7,10,13,16-hexaoxacyclooctadecane) alsonamed as 2,5,8,15,18,21-hexaoxatricyclo[20.4.0.0⁹,14 ]hexacosane.

Specific examples of other suitable macrocyclic polyether compounds(trivial names for simplicity) include 12-crown-4, monobenzo-15-crown-5,bis(4-t-butylbenzo)-21-crown-7, tetrabenzo-24-crown-8,monocyclohexano-27-crown-9, and 30-crown-10. The compounds are morecompletely disclosed in the cited references.

Any chromium-containing salt which is insoluble in nonaqueous solventswhich do not easily rehydrate the silica but which can form a complexwith the solubilizing agent such as the macrocyclic polyether compoundsand which is at least partially converted into chromium oxide whencalcined in an oxygen-containing atmosphere can be employed. Presentlypreferred chromium salts, however, are the chromates and/or dichromatesof ammonia, alkali metals and alkaline earth metals. The ammonium saltsare particularly preferred since after calcination only chromium oxideremains in the finished catalyst.

The type of solvents in which the chromium salts are initially insolubleare nonaqueous solvents which do not easily rehydrate the silica. Thisexcludes water and in general primary alcohols. Included in this classof solvents are hydrocarbons, halohydrocarbons, acetonitrile, and forthe most part ketones, tertiary alcohols and secondary alcohols. Aftersolubilization, the chromium salts are soluble in these solvents.

The salt/solubilizing agent complexes can be formed by combining thesolubilizing agent and the salt together in one of the nonaqueoussolvents which does not easily rehydrate the silica as definedhereinabove to thus convert the salt to a chromium-containingcomposition soluble in the solvent used to form the complex. Preferably,the resulting solution is used to impregnate the particulate supportwith the thus solubilized chromium salt, the solvent is evaporated andthe composite is calcined in a dry oxygen-containing atmosphere toactivate it for polymerization.

The use of the above described solubilizing agents such as crown ethersmakes it possible to anhydrously impregnate catalyst supports withchromium salts such as chromate or dichromate salts which are normallyinsoluble in nonaqueous solvents which do not easily rehydrate thesilica. This is useful in cases where the pore structure or surface ofthe support may be adversely affected by water or other solvents whicheasily rehydrate the silica.

The mole ratio of crown ether to chromium-containing salt can varydepending upon the cation content of the salt. Thus, when the salt is(NH₄)₂ CrO₄, about one mole of crown ether and about 0.5 mole of (NH₄)₂CrO₄ are employed in preparing the complex, i.e. one mole ofsolubilizing agent per equivalent of cation. A slight deficiency ofsolubilizing agent or a substantial excess can be tolerated, however,i.e. from 0.9 to 2 moles of solubilizing agent per equivalent of cation,for instance.

The activation is carried out in oxygen ambient such as air at atemperature generally within the range of 800° to 1832° F. (427° to1000° C.). However, one unexpected benefit flowing from the use of theinvention is that the catalysts reach a peak in melt index potential atessentially the same temperature as do aqueously impregnated chromiumcomposites, i.e. about 1500° to 1700° F. (816° to 927° C.) whichcompares with conventional anhydrously impregnated chromium compositionswhich reach a peak in melt index potential when activated at about 900°to 1200° F. (482° to 649° C.). Hence, a preferred activation procedureis to activate at 1500° to 1700° F. in air. Activation times aregenerally at least 5 minutes, preferably 1/2 to 10 hours, morepreferably 1 to 4 hours. Of course, the time and temperatures can beinfluenced by the percent of oxygen in the oxidation ambient.

The catalysts of this invention can be used to polymerize at least onemono-1-olefin containing 2 to 8 carbon atoms per molecule. The inventionis of particular applicability in producing ethylene hompolymers andcopolymers from mixtures of ethylene and one or more comonomers selectedfrom 1-olefins containing 3 to 8 carbon atoms per molecule. Exemplarycomonomers include aliphatic 1-olefins such as propylene, 1-butene,1-hexene, and other lower mono-1-olefins and conjugated or nonconjugateddiolefins such as 1,3-butadiene, isoprene, piperylene,2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene and other suchdiolefins and mixtures thereof. Ethylene copolymers preferablyconstitute at least 90, preferably 95 to 99 mole percent polymerizedethylene units. Ethylene, propylene, 1-butene, and 1-hexene areespecially preferred.

The polymers can be prepared from the catalysts of this invention bysolution polymerization, slurry polymerization, and gas phasepolymerization techniques using conventional equipment and contactingprocesses. However, the catalysts of this invention are particularlysuitable for ue in slurry polymerizations to produce polymer having agood balance of rheological properties such as melt index and responseto shear. Hydrogen can be used to further increase the melt index ifdesired. Temperatures for slurry polymerization, i.e., polymerization ata temperature where the polymer formed is predominantly insoluble in thediluent are about 66° to 110° C. (150° to 230° F.) for predominantlyethylene polymers.

EXAMPLE I--CATALYST PREPARATION

A sample of commercially available, dry silica-titania cogel containing2 weight percent titanium was calcined for 5 hours under fluidizingconditions with dry air, then cooled and stored in a desiccator untilready for further use.

The crown ether employed in preparing each catalyst wasdicyclohexano-18-crown-6. A solution of it in acetone was prepared bydissolving 2 g of the crown ether in 10 ml of acetone.

Catalyst A was prepared by contacting about 10 ml of acetone containing0.269 g of ammonium chromate with sufficient crown ether solution toprovide 1.32 g of the ether. The mixture was stirred about 16 hours(overnight) diluted to 30 ml with acetone and stirring continued brieflyto obtain a homogeneous solution. The solution was gradually added to7.1 g of the calcined silica-titania cogel with vigorous shaking to forma slurry. The slurry was dried on a hot plate under a stream of drynitrogen until a free-flowing product was obtained after which it wasstored in a desiccator until it was to be activated for ethylenepolymerization runs. The amount of chromium contained in the drycomposite was calculated to be 1.3 weight percent. Analysis of thecalcined catalyst gave a chromium content of 0.84 weight percent.

Catalyst B was prepared in the fashion employed above by admixing about10 ml acetone containing 0.223 g ammonium dichromate with sufficientcrown ether solution to provide 0.66 g of the ether. The mixture wasstirred and diluted as before. It was finally admixed with 6.3 g of thecalcined silica-titania cogel to obtain a slurry which was dried andstored in the manner previously described. The amount of chromiumcontained in the composite on a dry basis was calculated to be 1.4weight percent. Analysis of the calcined catalyst gave a chromiumcontent of 1.55 weight percent.

Catalysts A and B were separately activated for ethylene polymerizationby heating each sample in a 65 mm diameter activator tube underfluidizing conditions with dry air flowing at the rate of 42 standardliters per hour for 4 hours at 371° C. After activation each sample wascooled, recovered, and stored in a desiccator for future use. Catalyst Awas bright orange in color and Catalyst B was burnt orange in color.

A portion of each previously activated Catalyst A and B was separatelyheated for an additional hour in the activator with 42 standard litersper hour of dry air at 538° C. to obtain Catalyst A₁ which was brightorange in color and Catalyst B₁ which was dark orange-brown in color.

A portion of each previously activated Catalyst A₁ and B₁ was separatelyheated for an additional hour in the activator with 42 standard litersper hour of dry air at 649° C. to obtain Catalyst A₂ which was darkorange in color and Catalyst B₂ which was brown in color.

A portion of each previously activated Catalyst A₂ and Catalyst B₂ wasseparately heated for an additional hour in the activator with 42standard liters per hour of dry air at 760° C. to obtain Catalyst A₃ andCatalyst B₃ which were unchanged in color.

A portion of each previously activated Catalyst A₃ and Catalyst B₃ wasseparately heated for an additional hour in the activator with 42standard liters per hour of dry air at 871° C. to obtain Catalyst A₄which was brown-orange in color and Catalyst B₄ which was brown-green incolor.

All activated catalyst after cooling were stored in a desiccator untilready for the subsequent ethylene polymerization tests.

EXAMPLE II--ETHYLENE POLYMERIZATION

Ethylene was polymerized in each run by contact with the catalyst in astirred, stainless steel reactor of 2.0 liter capacity containing about1.5 liters of isobutane diluent. Each run was conducted at 107° C. witha reactor pressure of 550 psig (3.8 MPa) for a time sufficient to obtaina polymer yield of about 5000 g per g catalyst. Each run was terminatedby stopping the ethylene flow, flashing ethylene and diluent, andrecovering the polymer. The amount of catalyst employed in each run andthe results obtained are present in Tables IIA and IIB.

                                      TABLE IA                                    __________________________________________________________________________    Ethylene Polymerization, Supported Catalyst                                   Based on Ammonium Chromate - Crown Ether Complex                              Catalyst                                                                      Run   Activation Reaction Time, Min.                                                                     Productivity                                                                         Corrected                                                                           HLMI                                  No.                                                                              No.                                                                              Temp. °C.                                                                    Weight g                                                                           Induction                                                                           Polym.                                                                            g/g (a)                                                                              MI (b)                                                                              MI (c)                                __________________________________________________________________________    1  A  371   .0410                                                                               4    58  4490   0.66  50                                    2  A.sub.1                                                                          538   .0508                                                                              13    60  4960   0.74  53                                    3  A.sub.2                                                                          649   .0339                                                                              16    50  4840   1.9   46                                    4  A.sub.3                                                                          760   .0428                                                                              11    40  4390   3.0   43                                    5  A.sub.4                                                                          871   .0339                                                                              14    60  5070   3.4   42                                    __________________________________________________________________________     (a) Productivity, g polymer per g catalyst.                                   (b) Melt index corrected to a common productivity of 5000 g polymer per g     catalyst.                                                                     (c) Ratio of high load melt index (ASTM D 123865T, Condition F) to melt       index (ASTM D 123865T, Condition E).                                     

                                      TABLE IB                                    __________________________________________________________________________    Ethylene Polymerization, Supported Catalyst                                   Based on Ammonium Dichromate - Crown Ether Complex                            Catalyst                                                                      Run   Activation Reaction Time, Min.                                                                     Productivity                                                                         Corrected                                                                           HLMI                                  No.                                                                              No.                                                                              Temp. °C.                                                                    Weight g                                                                           Induction                                                                           Polym.                                                                            g/g    MI    MI                                    __________________________________________________________________________    6  B  371   .0450                                                                              long (d)                                                                            150 2700   0.35  60                                    7  B.sub.1                                                                          538   .0566                                                                              56    70  5190   0.80  65                                    8  B.sub.2                                                                          649   .0533                                                                              51    55  4830   1.3   56                                    9  B.sub.3                                                                          760   .0460                                                                              77    56  5020   1.8   50                                    10 B.sub.4                                                                          871   .0503                                                                              13    60  5030   3.6   44                                    __________________________________________________________________________     (d) In excess of 60 minutes.                                             

Inspection of the results given in the Tables show that active ethylenepolymerization catalysts are produced. The melt index values obtainedranging from about 0.3 to about 4 and HLMI/MI ratios ranging from 42 to65 are indicative of commercially attractive polymers which can beutilized in film, injection molding, blow molding and the like.

The data indicates that the melt index capability of catalysts A and Bare improved as the activation temperatures employed increase from 371°to 871° C. This behavior resembles that of chromium oxide-silicacatalysts prepared by admixing chromium trioxide with a silica-titaniahydrogel and removing water from the mixture by azeotrope drying withethyl acetate as disclosed in said U.S. Pat. No. 3,887,494.

The polymer melt index values shown in the Tables cannot be obtained byimpregnating the selected calcined silica-titania substrate with aqueoussolutions of either ammonium chromate or ammonium dichromate andrecalcining the mixtures to produce catalysts. Contact of the large poresupport with water has a deleterious effect and catalysts produced withthe water-treated supports have substantially diminished melt indexcapability.

The ammonium salts mentioned above are not soluble by themselves in theacetone employed in forming solutions of the crown ether-ammonium saltcomplexes. The use of such complexes dissolved in acetone, acetonitrile,hydrocarbons, halohydrocarbons, secondary alcohols, tertiary alcohols ormixtures thus affords a way of impregnating water-sensitive silicasupports with otherwise insoluble inorganic chromium-containing saltswhich are capable of forming complexes with a crown ether.

While this invention has been described in detail, it is not to beconstrued as limited thereby but is intended to cover all changes andmodifications within the spirit and scope thereof.

We claim:
 1. A process comprising:contacting a chromium-containing salt,which is insoluble in nonaqueous solvents which do not easily rehydratesilica, with a solubilizing agent thus converting it to achromium-containing complex having charged ions which is soluble in saidnonaqueous solvents; impregnating a particulate support with the thussolubilized chromium-containing complex dissolved in a nonaqueoussolvent which does not easily rehydrate silica; activating said thusimpregnated support by heating same in an oxygen ambient at atemperature sufficient to oxidize at least a portion of said chromium toproduce a catalyst; contacting at least one mono-1-olefin having 2 to 8carbon atoms per molecule with said catalyst under polymerizationconditions; and recovering a polymer.
 2. A process according to claim 1wherein said olefin is selected from ethylene, propylene, 1-butene and1-hexene.
 3. A process according to claim 1 wherein said olefin ispredominantly ethylene.
 4. A process according to claim 3 wherein saidcontacting under polymerization conditions is carried out at atemperature within the range of 150° to 230° F.
 5. A process accordingto claim 1 wherein said chromium-containing salt is selected fromchromates, dichromates and mixtures thereof.
 6. A method according toclaim 1 wherein said solubilizing agent is a crown ether.
 7. A methodaccording to claim 1 wherein said particulate support is asilica-titania cogel.
 8. A method according to claim 1 wherein saidactivating is carried out in air at a temperature within the range of1500° to 1700° F.
 9. A method according to claim 1 wherein saidchromium-containing salt is selected from ammonium chromate and ammoniumdichromate and wherein said solubilizing agent is a substituted orunsubstituted 18-crown-6 -macrocyclic polyether.
 10. A method accordingto claim 9 wherein said macrocyclic polyether isdicyclohexano-18-crown-6.
 11. A method according to claim 10 whereinsaid activating is carried out in air at a temperature within the rangeof 1500° to 1700° F.
 12. A method according to claim 11 wherein saidnonaqueous solvent is acetone and wherein said chromium salt iscontacted with said solubilizing agent by mixing the two together inacetone.
 13. A method according to claim 1 wherein said nonaqueoussolvent is selected from hydrocarbons, halohydrocarbons, acetonitrile,ketones, tertiary alcohols and secondary alcohols.